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为提高金属的活性,采用不同的纳米金属作水相Barbier-Grignard型反应的促进剂,通过还原方法制备球状纳米Sn、管状纳米Bi,通过溶剂分散法制备球状纳米In。在水相中化学计量纳米锡(铋或铟)成功地促进1 mmol苯甲醛与1.5～2.0mmol烯丙基(或烯丁基)溴反应,在短时间内得到了高产率的高烯丙醇。反应的活性、区域选择性、非对映选择性受不同种类纳米金属的影响。纳米锡促进的烯丁基化反应主要得到以anti-异构体为主的γ型产物;纳米铋促进的烯丁基化反应主要得到以syn-异构体为主的γ型产物;纳米铟促进醛和烯丁基溴的烯丁基化反应,得到了以anti-异构体为主的γ型产物。
In order to improve the activity of metal, spherical nano-Sn and tubular nano-Bi were prepared by reductive method using different nano-metal as promoter of aqueous Barbier-Grignard reaction. Spherical nano In was prepared by solvent dispersion method. Stoichiometric nano-tin (bismuth or indium) in the aqueous phase successfully promoted the reaction of 1 mmol of benzaldehyde with 1.5-2.0 mmol of allyl (or en-butyl) bromine in high yields in high yields of high allyl alcohol . The reaction activity, regioselectivity and diastereoselectivity are affected by different kinds of nano-metals. The isobutyrylation reaction catalyzed by nano-tin mainly yielded γ-type products mainly containing the anti-isomer. The nano-bismuth-promoted en-butyrate mainly got γ-type products mainly composed of syn-isomers. Promote the allylation reaction of aldehyde and en-butyl bromide to get γ-type product which is dominated by anti-isomer.